CA2357385A1 - Supported phosphinimine polymerization catalyst - Google Patents

Supported phosphinimine polymerization catalyst Download PDF

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Publication number
CA2357385A1
CA2357385A1 CA002357385A CA2357385A CA2357385A1 CA 2357385 A1 CA2357385 A1 CA 2357385A1 CA 002357385 A CA002357385 A CA 002357385A CA 2357385 A CA2357385 A CA 2357385A CA 2357385 A1 CA2357385 A1 CA 2357385A1
Authority
CA
Canada
Prior art keywords
catalyst system
metal oxide
group
aluminoxane
fluorided
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CA002357385A
Other languages
French (fr)
Other versions
CA2357385C (en
Inventor
Xiaoliang Gao
P. Scott Chisholm
Robert D. Donaldson
Ian Mckay
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nova Chemicals Corp
Original Assignee
Nova Chemicals Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to CA2357385A priority Critical patent/CA2357385C/en
Application filed by Nova Chemicals Corp filed Critical Nova Chemicals Corp
Priority to AU2002325742A priority patent/AU2002325742A1/en
Priority to JP2003528871A priority patent/JP2005502777A/en
Priority to EP02759998A priority patent/EP1427761A2/en
Priority to PCT/CA2002/001401 priority patent/WO2003025027A2/en
Priority to BR0212565-0A priority patent/BR0212565A/en
Priority to US10/244,194 priority patent/US6710143B2/en
Priority to CNB028182243A priority patent/CN1285622C/en
Priority to KR10-2004-7003824A priority patent/KR20040035793A/en
Publication of CA2357385A1 publication Critical patent/CA2357385A1/en
Application granted granted Critical
Publication of CA2357385C publication Critical patent/CA2357385C/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/642—Component covered by group C08F4/64 with an organo-aluminium compound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S526/943—Polymerization with metallocene catalysts

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
  • Polymerization Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)

Abstract

A phosphinimine catalyst for olefin polymerization is supported on a directly fluorided metal oxide with an aluminoxane. This catalyst is highly active for olefin polymerization in comparison to prior art catalysts which use non-fluorided metal oxide supports. The directly fluorided metal oxide may be conveniently prepared by contacting the precursor metal oxide with a simple alkali metal salt (such as NaF) in an aqueous slurry.

Claims (9)

1. A supported catalyst system for olefin polymerization comprising:
a) a directly fluorided metal oxide;
b) an aluminoxane; and c) a group 4 metal catalyst having at least one phosphinimine ligand.
2. The catalyst system according to claim 1 wherein said group 4 metal is selected from the group consisting of titanium, hafnium and zirconium.
3. The catalyst system according to claim 2 wherein said group 4 metal catalyst is defined by the formula:

wherein L1 is a phosphinimine ligand; M is selected from the group consisting of titanium, hafnium and zirconium; L2 is independently selected from the group consisting of cyclopentadienyl, substituted cyclopentadienyl and heteroatom ligands, with the proviso that L1 and L2 may optionally be bridged together so as to form a bidentate ligand; and wherein each L3 is an activatable ligand.
4. The catalyst system according to claim 3 wherein L2 is selected from cyclopentadienyl and substituted cyclopentadienyl; L1 is a phosphinimine ligand; n is 2 and each L3 is a halide.
5. The catalyst system according to claim 1 further characterized in that said metal oxide is silica and said aluminoxane is methylaluminoxane.
6. The catalyst system according to claim 5 wherein said directly fluorided metal oxide is further characterized by containing a fluorine concentration of from 0.01 to 10 weight % fluorine.
7. The catalyst system according to claim 6 wherein said aluminoxane is present in an amount of from 1 to 40 weight % based on the combined weight of said directly fluorided metal oxide and said aluminoxane.
8. The catalyst system according to claim 7 wherein the molar ratio of aluminum contained in said aluminoxane to transition metal M is from 10:1 to 200:1.
9. A process for olefin polymerization comprising contacting at least one olefin monomer with the supported catalyst system according to claim 1 under polymerization conditions.
CA2357385A 2001-09-17 2001-09-17 Supported phosphinimine polymerization catalyst Expired - Lifetime CA2357385C (en)

Priority Applications (9)

Application Number Priority Date Filing Date Title
CA2357385A CA2357385C (en) 2001-09-17 2001-09-17 Supported phosphinimine polymerization catalyst
JP2003528871A JP2005502777A (en) 2001-09-17 2002-09-16 Phosphinimine-supported polymerization catalyst
EP02759998A EP1427761A2 (en) 2001-09-17 2002-09-16 Supported phosphinimine polymerization catalyst
PCT/CA2002/001401 WO2003025027A2 (en) 2001-09-17 2002-09-16 Supported phosphinimine polymerization catalyst
AU2002325742A AU2002325742A1 (en) 2001-09-17 2002-09-16 Supported phosphinimine polymerization catalyst
BR0212565-0A BR0212565A (en) 2001-09-17 2002-09-16 Polymerization supported phosphinimine catalyst
US10/244,194 US6710143B2 (en) 2001-09-17 2002-09-16 Supported phosphinimine polymerization catalyst
CNB028182243A CN1285622C (en) 2001-09-17 2002-09-16 Supported phosphinimine polymerization catalyst
KR10-2004-7003824A KR20040035793A (en) 2001-09-17 2002-09-16 Supported phosphinimine polymerization catalyst

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CA2357385A CA2357385C (en) 2001-09-17 2001-09-17 Supported phosphinimine polymerization catalyst

Publications (2)

Publication Number Publication Date
CA2357385A1 true CA2357385A1 (en) 2003-03-17
CA2357385C CA2357385C (en) 2010-06-15

Family

ID=4169992

Family Applications (1)

Application Number Title Priority Date Filing Date
CA2357385A Expired - Lifetime CA2357385C (en) 2001-09-17 2001-09-17 Supported phosphinimine polymerization catalyst

Country Status (9)

Country Link
US (1) US6710143B2 (en)
EP (1) EP1427761A2 (en)
JP (1) JP2005502777A (en)
KR (1) KR20040035793A (en)
CN (1) CN1285622C (en)
AU (1) AU2002325742A1 (en)
BR (1) BR0212565A (en)
CA (1) CA2357385C (en)
WO (1) WO2003025027A2 (en)

Families Citing this family (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7534842B2 (en) 2005-11-16 2009-05-19 Chevron Phillips Chemical Company, Lp Catalysts for olefin polymerization
KR20130026531A (en) * 2010-02-22 2013-03-13 유니베이션 테크놀로지즈, 엘엘씨 Catalyst systems and methods for using same to produce polyolefin products
WO2013028283A1 (en) * 2011-08-19 2013-02-28 Univation Technologies, Llc Catalyst systems and methods for using same to produce polyolefin products
WO2015059268A1 (en) 2013-10-25 2015-04-30 Dsm Ip Assets B.V. Preparation of ultra high molecular weight polyethylene
ES2805362T5 (en) * 2013-10-25 2023-07-24 Dsm Ip Assets Bv Preparation of Ultra High Molecular Weight Ethylene Copolymer
US9441063B2 (en) * 2014-10-09 2016-09-13 Chevron Phillips Chemical Company Lp Titanium phosphinimide and titanium iminoimidazolidide catalyst systems with activator-supports
US9796795B2 (en) 2015-01-14 2017-10-24 Exxonmobil Chemical Patents Inc. Tetrahydroindacenyl catalyst composition, catalyst system, and processes for use thereof
US10717790B2 (en) 2015-04-20 2020-07-21 Exxonmobil Chemical Patents Inc. Catalyst composition comprising fluorided support and processes for use thereof
EP3274380B1 (en) 2015-04-20 2020-08-19 ExxonMobil Chemical Patents Inc. Catalyst composition comprising fluorided support and processes for use thereof
US10618989B2 (en) 2015-04-20 2020-04-14 Exxonmobil Chemical Patents Inc. Polyethylene composition
CN109312015B (en) 2016-05-03 2021-10-26 埃克森美孚化学专利公司 Tetrahydroindacenyl catalyst compositions, catalyst systems, and methods of use thereof
US9803037B1 (en) 2016-05-03 2017-10-31 Exxonmobil Chemical Patents Inc. Tetrahydro-as-indacenyl catalyst composition, catalyst system, and processes for use thereof
WO2018061865A1 (en) * 2016-09-28 2018-04-05 日本ゼオン株式会社 Method of manufacturing package structure
US10703838B2 (en) 2017-10-31 2020-07-07 Exxonmobil Chemical Patents Inc. Mixed catalyst systems with four metallocenes on a single support
US10899853B2 (en) 2018-03-19 2021-01-26 Exxonmobil Chemical Patents Inc. Processes for producing high propylene content PEDM using tetrahydroindacenyl catalyst systems
US10927207B2 (en) 2018-04-06 2021-02-23 Exxonmobil Chemical Patents Inc. Thermoplastic vulcanizate compositions
MX2021003372A (en) * 2018-09-27 2021-05-27 Chevron Phillips Chemical Co Lp Processes for producing fluorided solid oxides and uses thereof in metallocene-based catalyst systems.
WO2021011906A1 (en) 2019-07-17 2021-01-21 Exxonmobil Chemical Patents Inc. TIRES COMPRISING RUBBER COMPOUNDS THAT COMPRISE PROPYLENE-α-OLEFIN-DIENE POLYMERS
US11472828B2 (en) 2019-10-11 2022-10-18 Exxonmobil Chemical Patents Inc. Indacene based metallocene catalysts useful in the production of propylene polymers
WO2022155026A1 (en) 2021-01-12 2022-07-21 Exxonmobil Chemical Patents Inc. Asymmetric constrained geometry catalysts

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4077904A (en) 1976-06-29 1978-03-07 Union Carbide Corporation Olefin polymerization process and catalyst therefor
FR2546522B1 (en) 1983-05-25 1985-07-26 Ato Chimie PROCESS FOR THE PREPARATION OF A TRANSITIONAL METAL COMPONENT FOR A CATALYTIC SYSTEM FOR OLEFIN POLYMERIZATION
US5219817A (en) 1991-01-02 1993-06-15 Phillips Petroleum Company Fluorided aluminas, catalysts, and polymerization processes
US5219962A (en) 1991-01-02 1993-06-15 Phillips Petroleum Company Fluorided aluminas, catalysts, and polymerization processes
US5221720A (en) 1991-01-02 1993-06-22 Phillips Petroleum Company Fluorided aluminas, catalysts, and polymerization processes
US5221654A (en) 1991-01-02 1993-06-22 Phillips Petroleum Company Fluorided aluminas, catalysts, and polymerization processes
US5221655A (en) 1991-01-02 1993-06-22 Phillips Petroleum Company Florided aluminas, catalysts, and polymerization processes
CA2210131C (en) * 1997-07-09 2005-08-02 Douglas W. Stephan Supported phosphinimine-cp catalysts
FR2769245B1 (en) * 1997-10-02 1999-10-29 Atochem Elf Sa SOLID SUPPORT ACTIVATOR OF METALLOCENE CATALYZERS IN OLEFINS POLYMERIZATION, ITS PREPARATION PROCESS, CORRESPONDING CATALYTIC SYSTEM AND POLYMERIZATION PROCESS
WO2000012565A1 (en) * 1998-08-26 2000-03-09 Exxon Chemical Patents Inc. Highly active supported catalyst compositions

Also Published As

Publication number Publication date
CN1561349A (en) 2005-01-05
EP1427761A2 (en) 2004-06-16
AU2002325742A1 (en) 2003-04-01
CA2357385C (en) 2010-06-15
CN1285622C (en) 2006-11-22
WO2003025027A3 (en) 2003-05-30
WO2003025027A2 (en) 2003-03-27
KR20040035793A (en) 2004-04-29
JP2005502777A (en) 2005-01-27
US20030119661A1 (en) 2003-06-26
BR0212565A (en) 2004-10-13
US6710143B2 (en) 2004-03-23

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Effective date: 20210917